Lubricant additive



Patented Nov. 3, 1942 Meyer S. Agruss, Chicago, Hans Schindler,Evanston,- and George W. Ayers, In, Chicago, 111., assignors to The PureOil Company, Chicago, Ill.,-. I a; corporation of Ohio No Drawing.Application June 21, 1940;

' Serial No. 341,640

17 Claims.

This invention relates to lubricating oils and to processes forimproving their properties and more particularly to the production oflubricating oils having green fluorescense and other desirableproperties. 1

One of the objects of this invention is to provide petroleum lubricatingoil possessing a green fluorescence from oils normally deficient in thatproperty.

Another object is to provide a method paring a green bloom agent.

A further object is to provide a green bloom agent useful in imparting agreen fluorescence to oils normally deficient in that property. j i

A still further object is to provide a method of preparing lubricating,compositions possessing a green fluorescense from lubricants normallydeficient in that property.

Other objects and advantages will be apparent from the followingdetailed description.

Certain lubricating oils such as those derived from naphthenic and mixedbase crudes, while possessing good lubricating characteristics, are,

of prenevertheless, deficient in the property of bloom Pennsylvanialubricating oils are reddish brown by transmitted light and green byreflected light, thereby possessing what is known as a green bloom orfluorescence. The trade acceptance of oils having a green bloom issuperior to that of oils which'do not possess such a bloom and it istherefore desirable in certain cases to impart a green bloom to suchlubricating oils which are deficient in this property.

It has been discovered that a very satisfactory green bloom impartingmaterial may be prepared by condensing petroleum resins withhalogenated, preferably chlorinated,- hydrocarbons, particularly thosehydrocarbons of the paraffin series. Condensation may be effected by anyof the well known condensing agents such as metallic halides, especiallyaluminum'chloride. A convenient and economical source of suitableparaffin hydrocarbons is commercial paraflin wax or petrclatums. Theseproducts are obtained in the course of conventional refining methods asapplied to the manufacture of lubricating oils.

Petroleum resins preferable for the condensation reaction are thoseresins obtained from spent or partially spent adsorbents such as fullersearth whichhave been used in decolorizing operations on petroleum oilssuch as neutral oils, bright stocks and cylinder stocks. may beconveniently obtained by extracting the spent adsorbents with chloroformor a mixture of benzol and alcohol or similar solvents. In

Such resins order to reduce the amount of oil in the resins the spentadsorbent is preferably washed with petroleum naphtha prior to theextraction with benzol and alcohol or chloroform. The resin may bereadily separated from the solvent-resin solution by distillation and isobtained as a dark brown viscous fluid. .If the petroleum oil which isdecolorized by contact with the adsorbent contains excessive asphalticmaterial, it may be desirable to separate at least a portion of thisasphaltic material prior to contact with the decolorizing adsorbent.This may be readily accomplished by any of several well knowndeasphaltizing methods, for example, by the us of propane.

Suitable resins may also be obtained in the course of refining gasolineand similar lightdistillates produced by cracking hydrocarbon oils,particularly in the cracking of hydrocarbon oils at more elevatedconversion temperatures, such as approximately 1000 F. or higher and inthe refining of gasoline or similar boiling range material produced byconversion or polymerization of hydrocarbon gases. The gasoline orsimilar distillate is contacted with polymerizing catalyst such asfullers earth or similar adsorptive clay at elevated temperature inorder to selectively polymerize gum-forming and color-impartingconstituents contained therein to resins. These gum-forming orcolor-imparting constituents are usually diolefins which readilypolymerize and oxidize upon exposure to aid and/or light.

In the well known Gray process cracked gasoline vapors .are passedthrough a tower containing a bed of adsorbent clay at temperaturesranging from approximately 200-400 F. and the resulting resin-containingliquid withdrawn from y late by fractional distillation.

Suitable resins of a similar nature may also be obtained from thetreatment of cracked distillates with selective polymerizing agent suchas dilute sulfuric acid or cold concentrated sulfuric acid.

The methods hereinabove set forth for the selective polymerization ofgum-forming and colorimparting bodies in cracked distillates' are wellgenerally used is of the order of 0.1% to 10%, although there is noreason. why greater or lesser amounts cannot be used since the'additiveis itself a good lubricant.

While material prepared in accordance with this invention is extremelyuseful as a green bloom imparting agent, the material is also useful asa wax crystal modifying agent in the dewaxing of wax-bearing lubricatingoils and in depressing the pour point of mineral lubricating oils whenused in the amounts above indicated. It is also possible tosimultaneously impart green bloom and depress the pour point of certainoils,

approximately 10%. In general it is preferred to have approximately 10%to chlorine by weight. Temperature during chlorination was preferablycontrolled so as to be not substantially in excess of 300 F. Thechlorinated product was mixed in the proportion of two parts by weightof chlorinated product to three parts by weight of hydrocarbon resinobtained from partially spent decolorizing clay which had been used todecolorize Pennsylvania cylinder stock. This resin was obtained by firstwashing the-spent clay with naphtha to remove any oil that may have beenpresent and then extracting the naphthawashed clay with chloroform. Thechloroform was distilled from the resin-chloroform solution and theresin obtained as a dark brown, sticky fluid of approximately 1.02specific gravity and about 590 seconds Saybolt Universal viscosity at210 F. The chemical condensation of the chlorinated petrolatum and resinwas effected by adding 10% by weight based. on the resin, of

anhydrous aluminum chloride to the mixture as a condensation catalystand gradually heating to a temperature of approximately 200 F. to 220 F.This temperature was maintained until the reaction was complete, whichin this case was about forty-five minutes. The completeness of thereaction was readily determined by-the cessation of the evolution ofhydrogen chloride gas, This produces a reaction product that issubstantially free of combined chlorine. The temperature at which thecondensation reaction may be carried out may vary considerably, butpreferably should not exceed 300 F. Ordinary atmospheric pressure issatisfactory. The condensation reaction was carried out under conditionsof constant agitation in carbon tetrachloride which functigned solely asa solvent to diminish the viscosity of. the mixture. When the reactionwas complete, reaction products insoluble in the carbon tetrachloridesolution were re-- moved by water washing. The soluble reaction product;was readily separated from carbon tetrachloride by fractionaldistillation. This reaction product contained only a very small amountof chlorine which was present as an impurity due to incomplete removalin water washing.

The effect of the addition of additive prepared as set forth in thepreceding paragraph, on the bloom of a Gulf Coast lubricating oil wasdetermined. The oil prior to mixture with the additive possessed adefinitely blue bloom. After addition of 1.0% of additive the oilpossessed a green bloom. ,It is apparent that the shade ofbloomimparted. to oils may be varied with the amountof additive used.The amount of additive such as some wax-bearinglVlid-Continentlubricating oils which are deficient in green bloom and of relativelyhigh pour test.

The amount of aluminum chloride used may vary between wide limits, butin general it is preferred to use approximately 2% to 10% by weight ofaluminum chloride based on the resin.

The proportion of hydrocarbon resin to chlorinated petrolatum which maybe used may be varied between rather wide limits. In general it has beenfound that most satisfactory results were obtained by usingapproximately three parts of hydrocarbon resin to two parts ofchlorinated petrolatum.

The foregoing specific description is given by way of illustration onlyand not by way of limitation, the invention being limited only asindicated by the appended claims.

What is claimed is:

1. A lubricant possessing a green fluorescence comprising lubricatingoil normally deficient in green fluorescence and a minor portion ofpetroleum resin-halogenated hydrocarbon condensation product. I

2. A lubricant in accordance with claim 1 where the resin is obtainedfrom partially spent decolorizing adsorbent used in the decolorizationof hydrocarbon oils.

.3. A lubricant in accordance with claim 1 where the petroleum resin isobtained from selective polymerization of diolefin-containinghydrocarbon distillates.

4. A lubricant in accordance with claim 1 where th halogen is chlorine.

5. A lubricant in accordance with claim 1 where the proportion ofhydrocarbon resin to halogenated hydrocarbon is approximately 3 to 2.

6. A lubricant possessing a green fluorescence comprising lubricatingoil normally deficient in green fluorescenceand a minor portion ofpetroleum resin-chlorinated paramnic hydrocarbon condensation product.

"7. A lubricant in accordance with. claim 6 where the paraflinichydrocarbon is petrolatum.

8. A lubricant in accordance with claim 6 which contains 0.1% to 10% ofcondensation product.

9. A lubricant in accordance with claim 6 where the chlorinatedhydrocarbon contains approximately 10% to 25% chlorine.

10. Method of producing a green bloom lubricating oil which comprisesadding to petroleum lubricating oil normally deficient in green bloom,condensation product of halogenated hydrocarbon and petroleum resin.

11. Method in accordance with claim 10 where the halogenated hydrocarbonis chlorinated parafl1nic hydrocarbon.

12. Method in accordance withclaim 10 where the petroleum resin isobtained from partially 13. Method in accordance with claim 10 where thepetroleum resin isobtained from selective polymerization ofdiolefln-containing hydrocarhalogen with hydrocarbon, mixing thhalogenated hydrocarbon with petroleum resin and a condensation agent,heating the mixture to elevated temperature and maintaining thetemperature for a sufficient time to efiect condensation of thehalogenated hydrocarbon and petroleum resin and separatingvthecondensation product from the reaction mixture.

15. Method in accordance with claim l where paraflinic hydrocarbon.

v 16. Method in accordance with claim 14 where the halogen is chlorine,the chlorine comprises .10%'t0 25% by weight of hydrocarbon and theratio of hydrocarbon resin to chlorinated hydrocarbon is approximately 3to 2.

17. Method of imparting green bloom and reducing the pour test ofwax-bearing lubricating oil normally deficient in green bloom whichcomprises adding to said oil condensation product of halogenatedhydrocarbon and petroleum resin.

MEYER S. AGRUSS. HANS SCHINDLER. GEORGE W. AYERS, JR.

the'halogen is chlorine and the hydrocarbon is

